Chemical production of oxygen



Patented Sept. 23, 1947 CHEMICAL PRODUCTION ,OF OXYGEN Eugene O. Brimm, Kenmore, N. Y., assignpr to The Linde Air Products Company, a corporation of Ohio No Drawing. Application July 3, 1-942, Serial No. 449,683

11 Claims. 1

This invention relates to a novel chemical process tor extracting oxygen from a mixture ,of oxygen-with inert gas, more particularly for separating and collecting gaseous oxygen of high purity from the atmosphere. The invention is also concerned with a novel chemical contact mass for use in the process. More particularly, the invention relates to improvements on the process of Du Motay and Marechal disclosed in United States Patent 70,705 of November 12, 1867.

The processof Du Motay et a1. is performed by alternately passing air and steam through a closed retort over a hot alkali manganate or similar reaction mass having the ability to be oxidized :by the passage of air thereover, and thereaiter to be deoxidized and release gaseous oxygen dur n the passa o e m thereoverh versible reaction theoretically is:

steam an Various reaction masses maybe used in the process, as disclosed by Du Motay et al., including the manganates and permanganates of potassium, sodium, or barium, as well as th chromates and ferrates of these metals, and in general all metallic acids or oxides forming, with potassium, sodium, or barium, binary combinatiops capable of becoming super-oxidized, and also possessing the property of releasing their oxygen at a temperature more or less elevated when they are placed in the presence of a current of steam. During the passage of steam over the hot mass, the gaseous oxygen is collected while the residual steam is condensed and separated from the oxygen. Oxygen of 95% purity or better may be obtained by this process. Of ,course the nitrogen residue from the air phase of the cycle also may be collected, if this is desired.

The basic process of Du Motay et a1. has not been commercially successful in competition with ther methods of producing oxygen because of several disadvantages rendering the process economically unprofitable. One of the principal drawbacks of the Du Motay et a1. process is the instability of the reaction mass, which deteriorates rapidly after being in service only a short time, with a resulting low oxygen production based on the quantities of air and steam passed over the mass. Moreover, the process consumes huge quantities of steam for the production of oxygen on a large scale, thus making the cost of operation prohibitive. Another serious disadvantage is the relatively great size and cost of the equ pme and plan r uired iQr Produc n xygen n a large scale, necessitat n a ar e ini a n estm nt.

Several attempts have been made by subsequent investigators to improve the fu l lamental Du Motay et ,al. process to, permit the production of ox en onomi fly. Devel pme t has be n mainly aimed at improving the ph sical or ch mical character of the rea tion mass for. better stab ity n g ea emci ncy of oxy n producti mo the be kno of t e e mprovew n is that prop sed by Geor e aszner n United States Patent 1,015,566, of January 23, 1912. Kaszner teaches the addition to the alkali manganate mass of an alkali meta-plumbate, such as sodium meta-plumbate, for increased stability. Despite the alleged improvement in the stability of the reaction mass, however, there is no substantial increase in the eificiency of oxygen production based on the quantities of steam and air supplied to the mass, excessive quantities of steam being required for oxygen production on a large scale. Eurthermore, experiments have shown tha eper's Pl mrosah hnihpi mass i wi h uns b e a f l he gra u l rel t n- Zafiion 0f ad co m nes hem h mes h ih eratiq at h g mperatu es T inci l bj t f the pre en i r hti h th n i is t Pr v de R0Y 1 m 93l mass r ex r t n cx g n rom a m x ur tficxlygen wi h n r gas he itieh a l e 'h hli h y h f om. W Wi D H th QQQQYQQWE? of h Pr a e ses scu sed ahh hPPh obje t is e f ori iqnc a n yel r zqqessio 9. ducing oxygen by the alternate passage of air and tea over a ho contac wher by improved ield of c r eh are hieiheda othe object is the provision of such a process which Wi1l11 m n91 i 1 ve a ong period hi time. Still another object is the provision of novel cona mass wh c g v an mannere .cqmh 'heti i high vh yser yi ld and seed stahi i when new an an: a e pas a ternate y ove he masses. An the Ob ct is to provide? hpve process ior preparing the novel ,cqntact mass so asio Rmv e n a hxygen sldfih ov ethe ob e nd the hhv l features of the invention, will become apparent rom t e f lcwi detai ed sc pt n Generally, the process of this invention comprises passing flowing streams alternately of air and steam over a hotsolid manganate type contact mass which is a sintered material comprising complexes of manganese, oxygen, silicon, and an alakali metal. The mass has a composition and relationship of elements such as theoretically contact mass, 30 grams of SiOz were mixed with to form a double manganate-metasilicate salt yX2MnO4.X2SiO3 or yX2MnO4.X2SiO3.X2O, wherein X is an alakli metal and y is from 2 to 4. The alkali metal is in excess of the amount required in the double salt by an amount substantially just sufiicient theoretically to combine with any other uncombined acidic materials in the mass. mass is oxidized during the passage of air thereover, and the oxygen is subsequently liberated from the mass and passes off with residual steam during the steam phase of the process. The residual steam then is condensed and the gaseous oxygen collected for immediate or future use. The cycling of air and steam over the contact mass may be continued indefinitely as long as the contact mass remains reasonably stable. It has been found that with this process, wherein an oxide or salt of silicon is added to the mixture for producing a contact mass, greatly improved yields of oxygen are obtained coupled with a mass stability at least as good as that of the Plumboxan mass of the Kaszner patent, and better than that of the Du Motay simple manganate contact mass.

In. one specific form of contact mass used in the process of the invention, just enough of the sodium or potassium hydroxide is added theoretically to react stoichiometrically with all of the oxide of manganese and all of the silicon compound to form, when sintered, sodium or potassium manganate and metasilicate.

(60.7%. Mn) and 209 ture sintered at 1600 F. Samples of the re- The sulting mass, having theoretically the formula 4Na2MnO4.Na2SiO3 (based onv the quantities of components added to form the mixture), were cycled with air and steam at about 1200 F. and at about 1290 F. for 10 minute cycles (5 minutes to each phase) at about atmospheric pressure.

For equal weights of samples oxygen yields of 186 cc. and 195 cc. were obtained at 1200 F. a

and 1290 F., respectively.

In a modified form of contact mass, an excess of the oxidic compound of the alkali or alkaline earth metal is added to the mixture before sintering. The amount of the hydroxide which gives the best results is that required? stoichiometrically to produce a compound having the theoretical formula 4Na2MnO4.Na2SiOs.Na2O,. although there is no evidence that this compound is actually obtained. Better oxygen yields were obtained with silicon catalysts when the masseswere prepared at 1470 F. than when they were:

prepared at 1830 F. or 2190 F.

The results with masses having various ratios? of manganese to silicon, and the effect of excess sodium hydroxide on the masses, are illustrated! in the following table, showing the results of tests made by alternately passing air. and steam over equal weights of samples under similar conditions:

The at 1290" F. and atmospheric pressure.

Sintering Oxygen Theoretical Formula Atomic Ratio Tempera- Yield ture cc./Samp1e OF 2N212M1104.N3.2Si05 GNa 2Mn 1Si 1, 690 210 4NazMI1O4.N3zSiO3 lONa 4Mn 1Si 1,600 222 4Na MnO .Na SiO .Na O 12Na. 4Mn 1Si l, 530 182 quantity of the hydroxide added to react with the oxide of manganese is based on the assumption that the components react completely with one another to form the compounds NazMnOi or KzMnOi. The quantity of the hydroxide added to react with the oxide or salt of silicon is calculated on the assumption that the compounds NazSiOs r KzSiOs are obtained. It is known, however, that in reality only a small part of the components react with one another to produce these definite compounds and the balance of the mass may consist of a heterogeneous mixture of complex and simple salts and oxides of manganese with salts and oxides of silicon. No exact chemical formula may be assigned to any mass because of this heterogeneity. For simplicity, however, such masses are usually termed manganate type masses.

The masses may be prepared with atomic ratios of anywhere between 2 and 4 atoms of manganese to 1 atom of silicon. For example, when preparing a contact mass on the basis of an atomic ratio of 2 to l, the quantities of the components mixed together are based on the theoretical formation of a double manganate-metasilicate salt having the formula 2Na2MnO4.Na2SiO3, although there is no evidence that such a compound actually is formed. For an atomic ratio of 4 to 1, the components are mixed together on the basis of the formula 4NazMnOi.NazSiO3. Atomic ratios of 4 to 1 have been found to give the best results in practice.

In a typical example of the preparation of a The following table shows examplesillustrating the superiority of compounds of silicon over several other compounds for addition to manga nate contact masses.

to each phase) at about atmospheric pressure.

The contact masses were tested all under similar conditions by passing air and steam alternately over samples of equal. weight at 1200 F. for 10 minute cycles (5 minutes,

. Oxygen Atomic Ratio In Smtenng Addition 0 Yield Mass Temp, F. (cg/Sample),

2Mn 1Si l, 690 4Mn 1Si l, 600 186'- lMn 1Pb 1, 700 32 2M11 1Pb 1, 740 59' 4Mn 1Pb l, 740 55 2Mn lBi l, 350 S4 2Mn his 2, 140 6 2Mn lSn 2, 190 66 21W]: 1V 2, 080 12 2Mn 1W 1, 510 58 2Mn 18b 2, 080 10 2Mn 1P 2, 070 15 enemas some cases are even more startling in theirsuperiority over prior known'processes when the air andsteam aremaintained at pressures above 1- /2 atmospheres absolute, and preferably at higher pressures such as 75 lb./sq. in. gauge. When the process is so operateda marked increase in'the stability of the contact mass'is noted, the oxygen yield increases in direct proportion to the absolute atmospheres of pressure, and the quantity of steam required is greatly reduced.

In one example of the operation of the process with steam and air under pressure, one ton of manganese dioxide ore, containing 47.36% manganese, 11.74% available oxygen and 11.74%

' silica, was reduced in a direct fired .gas furnace to an available oxygen content of 6.26%. This reducedore was then mixed with sodium hydroxide'to'producea mixturecontaining 42% sodium hydroxide and 58% reduced ore, and the mixture sintered at 1200 C. The resulting mass showed by-chemical analysis a sodiumlto manganese ratio of 8 to 6, with sufficient excess sodium toreact with the silica present.

A sample of the mass then was cycled with steam and air alternately at a temperature of 1200 F. and a pressure of 75 lb./sq. in., giving an oxygen yield of 0.52 cu. ft./hr. at a constant rate over a continuous periodoftwenty days.

No satisfactory theory has been developed to explain the superior results obtainable when oxides or salts of silicon are-used with manganate type contact masses. Kaszner, in his Patent 1,015,566, advanced the theoiy that his plumbate reacted with free alkali liberated during the steam phase of the process and prevented segregation of, alkali from the rest of the mass. There is no strong evidence, however, that this theory is correct. Moreover, there is no evidence that the oxides or salts used according to this invention act in the same way as does the plumbat of Kaszner, irrespective of whether Kaszners theory is or is not correct.

What is claimed is:

1. A sintered solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and air, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and sodium, said mass having a composition and relationship of the elements corresponding approximately to 4 mols of Na2MnO4 to 1 mol of Na'iSiOs to 1 mol of NazO.

2. A process for extracting oxygen from a mixture of oxygen with inert gas comprising alternately passing flowing streams of said mixture and steam into contact with a sintered solid hot manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and oxygen, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and sodium, said mass having a composition and relationship of the elements corresponding approximately to 4 mols of NazMnOr to 1 mol of NazSiOs to 1 mol of NazO, said oxygen being liberated from said mass during the passage of steam.

3. A process for producing a contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and air, respectively, which process comprises sintering together at a temperature below 1830 F. an intimate mixture of sodium hydroxide, an oxide of manganese, and a compound selected from the group consisting of oxides and salts of silicon in proportions such as to form theoretically 4. .Asolid manganate type contact mass characterized by its ability to be deoxidized and oxidizedalternately bysteam and air, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and an alkali metal, said material having a composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt yX2MnO4.X2SiO3, wherein X is an alkali metal and y is from 2 to 4, said alkali metal being in excess of the amount required in said double salt by an amount substantially just suificient theoretically to combine with the other uncombined acidic materials in the mass.

5. A solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and air, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and an alkali metal, said material having a composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt 4XzMnO4.'X2SiO3, wherein X is an alkali metal, said alkali metal being in excess of the amount required in said double salt by an amount substantially just sufiicient theoretically to combine with the other uncombined acidic materials in'the mass.

6. A solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and air, respectively, said mass being asintered material comprising complexes of manganese, oxygen, silicon, and sodium, said material having a, composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt tljNazMnOhNazSiOa, wherein y is from 2 to 4, said sodium being in excess of the amount required in said double salt by an amount substantially just suificient theoretically to combine with the other uncombined acidic materials in the mass.

7. A solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and air, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and potassium, said material having a composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt yK2MnO4.KzSiO3, wherein y is from 2 to 4, said potassium being in excess of the amount required in said double salt by an amount substantially just sumcient theoretically to combine with the other uncombined acidic materials in the mass.

8. A process for extracting oxygen from a mixture of oxygen with inert gas comprising alternately passing streams of said mixture and steam over a hot solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and oxygen, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and an alkali metal, said material having a composition and relationship of elements such as theoretically to form a double manganate-meta silicate salt yX2MnO4.X2SiO3, wherein X is an alkali metal and y is from 2 to 4, said alkali metal being in excess of the amount required in said double salt by an amount substantially just sufficient theoretically to combine with the other uncombined acidic materials in the mass.

9. A process for extracting oxygen from a. mixture of oxygen with inert gas comprising alternately passing streams of said mixture and steam over a hot solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and oxygen, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and an alkali metal, said material having a composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt 4X2MnO4.X2SiO3 wherein X is an alkali metal, said alkali metal being in excess of the amount required in said double salt'by an amount substantially just sufiicient theoretically to combine with the other uncombined acidic materials in the mass. 1

10."A process for extracting oxygen from mixture of oxygen with inert gas comprising a1 ternately passing streams of said mixture and steam over a hot solid manganate type contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and oxygen, respectively, said mass being a sintered material comprising complexes of manganese, oxygen, silicon, and sodium, said material having a composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt yNa2MnO4NazSiO3 wherein y is from 2 to 4, said sodium being in excess of the amount required in said double salt by an amount substantially just sufficient theoretically to combine with the other uncombined acidic materials in the mass.

11. A process for extracting oxygen from a mixture of oxygen with inert gas comprising alternately passing Streams of said mixture and steam over a hot solid manganatetype contact mass characterized by its ability to be deoxidized and oxidized alternately by steam and oxygen, respectively, said mass being a sintered material comprising complexes of manganese, oxygen,

8 silicon, and potassium, said material having a composition and relationship of elements such as theoretically to form a double manganate-metasilicate salt yK2MnO4.K2SiO3 wherein y is from 2 to 4, said potassium being in excess of the amount required in said double salt by an amount substantially just sufiicient theoretically to combine with the other uncombined acidic materials in the mass.

EUGENE O'. BRIMIM.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 500,697 Webb July 4, 1893 515,443 Parkinson Feb. 27, 1894 1,124,304 Danckwardt Jan. 12, 1915 1,303,911 Jorgensen May 20, 1919 1,694,122 Jaeger Dec. 4, 1928 2,086,507 Larsen July 6, 1937 2,154,128 Jacobs Apr. 11, 1939 2,176,774 Sweet Oct. 17, 1939 FOREIGN PATENTS Number Country Date 14,925 Great Britain 1890 3,034 Great Britain 1891 13,959 Great Britain 1895 OTHER REFERENCES Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, Longmans, N. Y., 1932, vol. 12, p. 246.

Phillips, Mineralogy, The Macmillan Co., New York, 1912, pp. 501 and 502. 

